Process for refining the raw oil of turpentine



' or halogens.

at low temperature.

Patented Apr. 22, 1930 UNITED STATES PATENT OFFICE.

FRIEDRICH SCHLOSSER, OF HOCHST-ON-THE-MAIN, AND MAX PAQUIN, OF KOENIG- STEIN IN TAUNUS, GERMANY, ASSIGNORS TO I.

G. FARBENINDUSTRIE AKTIEN- GESELLSCHA.F'1, OF FRANKFOBT-ON-THE-MAIN, GERMANY PROCESSFOR BEFINING THE RAW OIL OF TURPENTINE No Drawing. Application filed August 31, 1925, Serial No. 53,742, and in Germany September 12, 1924.

The present invention relates to a process for refining the raw oil of turpentine produced in the manufacture of synthetic camphor.

In the manufacture of synthetic camphor a raw oil of turpentine is produced for which a technical or industrial use can be found only .with difiiculty on account of its disagreeable and pungentodor and its undesirable drying properties.

distillation and attempts have been made to utilize the several fractions, i.- e., the fraction which boils at low temperature and does not resinify substantially when' evaporated, and the fraction which contains resinifying constituents and boils at high temperature. The said fractions, however, show also the disadvantages above mentioned so that. a technical or industrial use for them can be found only with difficulty.

Nowwe have found that products of technical value can be obtained from the raw turpentine oil produced in the manufacture of synthetic campho'r by treating the said oil with acids or alkalies or oxidizing agents We Wish to state that by the term turpentine oil we mean either the whole turpentine oil or any of its fractional distillation products. The treatment of the turpentine oil may take place in the cold or odor of'the product is thereby rendered milder and more agreeable. By varying the duration or intensity of the treatment one may obtain products-of which the quantlty ofthe high-boiling and resinifying fraction is 1ncreased at the expense of the fraction boiling The low-boiling fraction which evaporates substantially without resinifying may be used as a erfect substitute for oil of turpentine, w ile the highboiling and resinifying fraction is an excellent substitute for linseed oil.

The process may be carried out in such a way that the' whole of the oil produced by the camphor process is subjected to a'treatment with acids ,"etc., whereupon the product formedis subjected to a fractional distllla- This raw oil of turpentine has been subjected to a fractional.

I pentine tion. Thus fractions are obtained similar re spectively to oil of'turpentine and linseed oil. .Another method consists in subjecting the raw oil to a fractional separation and then treating thefractiona-l portions so obtained separately in an oxidizing, etc., manner. The process thus may beexecuted in one or the other way according to the requirements of the industrial market; v

The following examples illustrate the .invention, the parts being by Weight.

1. 400 parts of decamphorated oil of turpentine are treated while stirring Well with 45 parts of sulfuric acid (s eclfic gravity 1.48) which are addedgradua 1y. Care must be taken by cooling that the temperature does not rise above 35-40 Centigrade. At the end of 5 hours the mass is washed with Water until neutral reaction is shown. By fractionation there is obtained (apart from a small residue). a substantially non-resinifying product as Well as a resinifying product.

pentine oil, the second product is an oil of a high boiling point and may be used, owing to its goods siccative properties, as a substitute for linseed oil.

If a relatively large quantity of the substitute for turpentine oil is desired, the said method is advantageous.

' 400 parts of the non-resinifying fraction of the decamphorated oil of turpentine are treated according to Example'l. The resulting reactionproduct may be divided into several fractions.

The main fraction possesses a mild and agreeable odor and may be used as a substitute for the oil of turpentine; The raw reaction product when washed shows a feeble coloration and is entirely free of acid; it may likewise be used for technical and industrial purposes without a previous fractionation in asimilar way as the main fra-ction. I

.3. 400 parts of decamphorated oil of turare treated while stirring with 30 parts of sulfuric acid (specific gravity 1,48) which are slowly added. The temperature is tion product there may be obtained for in stance two fractions in the proportion of 34%, boiling point 120-200 C. 63%, boiling point 200350 C.

The product obtained from the low-boiling fraction alone thus mainly consists in the resinous and high-boiling product which may be used as a substitute for linseed oil without fractionation.

' 5. 400 parts of the high-boiling resinifying fraction of the decamphorated oil of turpentine are treated while stirring with 45 parts of sulfuric acid it is washed with water and heated to 160 C. for eliminating small quantities of water. The product obtained has a very mild odor and may be used directly or after a previous distillation as an excellent drying substitute for linseed oil.

- air while boiling in a reflux apparatus. Ac-

current of chlorine. When the cording to the time of reaction mixtures are obtained containing more or less increased high-boiling fraction of a mild and agreeable odor.

By the use of strongly acting for. instance spongy platinum, of strongly oxidizing gases, for instance oxygen, there is obtained apart from a considerable increase of the resinifying fraction an essentially lighter shade in color.

The operation according to Examples 6 and 7 may be applied to the resinifying'fraction alone or to the non-resinifying fraction alone in the same manner as well asunder pressure at a high temperature.

8. 400 parts of the low-boiling, non-resinifying fraction of the decamphorated oil of turpentine are treated while cooling with'a or by the use finished, it is washed with a strongly diluted solut on of sodium carbonate. 92% of the I'GL'JiZlOIi product boils at 155200 'centigrade,

carbon or ultramarine for (specific gravity 1,52) When the oil has cleared up after three hours mild odor is obtained which may be used catalyzers,

sa turation is 8% of the same at 200250 centigrade. The

content of chlorine is 10,1% on the average. The product obtained may be widely used as adiflicultly burning solvent of high-boiling point. r

'9. Into a residue of an oil of turpentine obtained 'by distilling off the low-boiling nonresinifying fraction there is introduced oxygen in a closed vessel for'5 to 6 hours at a temperature of. about 140450 centigrade. A polymerization of the oil takes place. The drying capacityof the residue is improved in such a way that a useful substitute for linseed oil is obtained. y

. An addition of about 10% of wood-oil increases the powerof drying and resistance of the oil-film.

By mixing the oil, thus treated, with coloring substances, such as ferric oxide for producing red shades, lithopone or barite with producing gray or blue shades, tained.

When the resulting residue from the oil of a variety of colors may be ob- V plate, it becomes uniformly resinous after 4 days and after 6 days so dry that it almost loses its stickiness, whereas the starting material resinifies only very unevenly and only after 8 days becomes so dry as to almost lose its stickiness.

When the residue from the oil of turpentine in first treated as above indicated and there is then added thereto 0,5% of a siccative substance (lead and manganese siccative) it becomes uniformly resino'us after 2 days and after 4 days so dry as to lose its stickiness.

By the processes above specified it is possible to obtain a. pure linseed oil varnish of a great drying-power without having to add any linseed oil.

For preparing oil paints, the residues from oil of turpentine, after being previously treated as above indicated, are mixed and stirred with the respective coloring substances in the proportion of 1: 1. The colors thus may be beautified in the usual manner and rendered still more resistant to atmospheric influences by adding thereto a small quantity of wax or stearin pitch or the like.

Having now described our invention what we claim is: y 1. Process for refining thegresidue of oil of turpentine produced in the manufacture turpentineproduced in the manufacture of of about 35 90 C. I

immee of synthetic camphor which comprises treuting the residue with a strong mineral acid.

2. Processfor refining the residue of oil of synthetio ee'niphor which comprises treating the residueqawith sulfuric acid.

3. The process for refining the residue of oil of turpentine produced in the manufacture of synthetic camphor which comprises treatin the residue with sulfuric acid of a. spe c' c gravity of about 1.48 at a temperature In testimony, whereof, we e'fix our si nstures. 1 

